Cation mobilities in liquid and supercritical C1–C4 hydrocarbons

The relationship between ion mobility and liquid viscosity is commonly expressed as μ [Formula: see text] η−m. In hydrocarbons the value of m tends to be near 1.0 at η > 5 mP, m > 1.0 at ~5 < η < 1 mP, and m < 1.0 at η < 0.5 mP. Thus there is a maximum in a plot of μη against η−1 and Walden's rule (m = 1.0) is only a rough approximation. The decrease of μη as the critical region is approached is accompanied by an increase in the ratio of diffusion coefficients Dmolec/Dion. Ion mobilities in the liquids well below their normal boiling points are chiefly controlled by the fluidity. At higher temperatures and concomitant lower liquid densities and viscosities μη first increases, due to an increasing ion mean free path, then decreases as the critical region is approached, due to the increasing liquid compressibility and consequent electrostriction about the ion.